Prepolymer reaction with diol

Following this work, the y -12F-diol was used for the direct reaction with hexamethylene-1,6-diisocyanate in the presence of dibutyltin dilaurate to produce a cross-linked elastomer or a reactive prepolymer which was terminated with either isocyanate or hydroxyl groups, depending on which reactant was in excess (142,143). 

Polyurethane adhesives are known for excellent adhesion, flexibihty, toughness, high cohesive strength, and fast cure rates. Polyurethane adhesives rely on the curing of multifunctional isocyanate-terrninated prepolymers with moisture or on the reaction with the substrate, eg, wood and ceUulosic fibers. Two-component adhesives consist of an isocyanate prepolymer, which is cured with low equivalent weight diols, polyols, diamines, or polyamines. Such systems can be used neat or as solution. The two components are kept separately before apphcation. Two-component polyurethane systems are also used as hot-melt adhesives. 

To obtain the polyurethanes, typically a prepolymer was first prepared by reacting the diisocyanate with various diols in dimethylformamide or dimethylacetamide in a two to one molar ratio at 100-110°C for two hours under nitrogen atmosphere. A solution of chain extenders, such as BEP, was then added to the prepolymer reaction mixture and further reacted another three hours. The polymer was isolated by quenching the reaction mixture in cold water. Fine white powder was obtained with a typical yield of around 90%. 

The block lengths and the final polymer molecular weight are again determined by the details of the prepolymer synthesis and its subsequent polymerization. An often-used variation of the one-prepolymer method is to react the macrodiol with excess diisocyanate to form an isocyanate-terminated prepolymer. The latter is then chain-extended (i.e., increased in molecular weight) by reaction with a diol. The one- and two-prepolymer methods can in principle yield exactly the same final block copolymer. However, the dispersity of the polyurethane block length (m is an average value as are n and p) is usually narrower when the two-prepolymer method is used. 

The chemical reaction proceeds with the terminal isocyanate of the initial prepolymer reacting with the available hydroxyl groups of the diol. This is illustrated in Figure 2.26. 

Soft blocks are composed of linear, dihydroxy poly ethers or polyesters with molecular weights between 600 and 3000. In a typical polymerization of a thermoplastic polyurethane elastomer, the macroglycol is end capped with the full amount of aromatic diisocyanate required in the final composition. Subsequently, the end-capped prepolymer and excess diisocyanate mixture reacts further with the required stoichiometric amount of monomeric diol to complete the reaction. The diol links the prepolymer segments together while excess diol and diisocyanate form short hard-block sements, leading to the (AB)n structure illustrated in Figure 1. Block lengths in (AB)n polymers are frequently much shorter than those in anionically synthesized ABA block copolymers. 

The elastomeric polymer is obtained by extending the prepolymer through its reaction with short-chain diols such as butanediol or diamines such as ethylene diamine, thus completing the formation of hard groups between soft, flexible chains. When amines are used, the final step is typically done in a polar solvent such as dimethyl acetamide. The conversion of these polymers into usable fibers may be accomplished by wet-, dry-, or melt-spinning operations, depending on the polymer. Additives to impart whiteness or improve resistance to ultraviolet radiation and... 

Effective catalysts for preparing the polyformals were p-toluenesulfonic acid, camphorsulfonic acid, methanedisulfonic acid, and perchloric acid. Various other acidic compounds were evaluated as catalysts with tetramethylcyclobutanediol. In these experiments, 0.5 to 1.0 gram of acidic compound per mole of tetramethylcyclobutanediol was normally added. If insufficient water was obtained, more catalyst was added. If the prepolymer was obtained but an appreciable amount of brown color was present, less catalyst was then used. Compounds which did not catalyze the reaction (no water obtained) were phosphoric acid, zinc chloride, trifluoroacetic acid, and heptafluorobutyric acid. Incomplete reactions (insufficient water) took place with concentrated hydrochloric acid, concentrated nitric acid, zinc fluoroborate, or Amberlite IRC-50 ion exchange resin as catalyst. A prepolymer was obtained when boron trifluoride etherate was used, but buildup did not take place in the solid phase (catalyst probably too volatile). Brown or speckled-brown polymers (after solid-phase buildup) were obtained with catalysts containing sulfonic acid groups (benzenesulfonic, dodecylbenzenesulfonic, sulfo-acetic, methanetrisulfonic, sulfuric, p-toluenesulfonic, camphorsulfonic, and methanedisulfonic acids). To obtain white polymers from tetramethylcyclobutanediol it was necessary to treat the solvent and prepolymer reaction mixture as previously described. (White polyformals were obtained from the other diols without this treatment.)... 

The prepolymer (1) above has two reactive end groups. Further polymerization can therefore be brought about by coupling with bifunctional reagents such as diamines, diols and also water. The reaction with a diamine gives the pol)rmer (2) which can be dissolved in dimethylforma-mide or dimethyl acetamide and then dry-spun to give elastomeric fibres. 

Reaction with difunctional amines (see the next paragraph) allows the formation of poly (urethane-co-urea) and further extends the versatility of the segment architecture. For further control of the structure, a prepolymer is formed. The reaction, such as the polyurethane reaction shown above, is carried out with excess di-isocyanate so that an isocyanate-terminated prepolymer is obtained. The isocyanates used are typically aromatic, such as toluene di-isocyanate. This prepolymer is then reacted with a short-chain diol or diamine (for a polyurea) to form the final polymer. 

Scheme 1.10. Formation of urethane prepolymer and subsequent reaction with a diol or diamine extender to give a polyurethane or a polyurethane-polyurea. Adapted from Hepburn (1982).

Prepolymers of polybutadiene diol (M. 2500), polytetramethylene oxide diol (M. 1400 and M. 2100), and prepolymer of polypropylene oxide diol (M. 1400) were used to obtain segmented elastomers SPU-1 to SPU-5. Prepolymers were prepared by reaction of appropriate diol with 2,4-toluene diisocyanate (2 moles per one mole of diol). Prepolymers of polytetramethylene oxide diol (elastomers SPU-1 and SPU-4) were cured by methylene-bis-o-chloroaniline, MOCA, or by mixture of MOCA and polytetramethylene oxide diol (SPU-2 and SPU-3). SPU-5 samples, prepared from prepolymer of polypropylene oxide diol, were cured by MOCA, and prepolymer of polybutadiene diol was cured by a mixture of MOCA and polytetramethylene oxide diol (SPU-6). Various concentrations of hard segments, Cj, in SPU were set by a ratio of mixture components and molecular weight of prepolymer (Table 10.14). Excess of NCO-groups was in the range 1.03-1.06 for SPU-1 to SPU-5 and 0.99 for SPU-6. All samples were cured at 80°C for 4 days. The... 

The principal of formation of this type of polyurethane elastomer medium, based on a cationic urethane latex, is where an isocyanate-terminated prepolymer derived from either a polyester or polyether diol and toluene diisocyanate is first chain-extended with an alkyl diethanolamine to yield a relatively low molecular weight urethane capable of further chain-extending reactions. Emulsification occurs when the partially extended urethane is added with high-speed mixing to 3% aqueous acetic acid. Curing of the latex takes place either by reaction of water with the terminal isocyanate groups or by reaction with water-soluble diamines. 

Four different processes are currently used to produce spandex fibers commercially melt extrusion, reaction spinning, solution dry spinning, and solution wet spinning. As shown in Figure 5, these processes involve different practical applications of basically similar chemistry. If the diol or diamine(s) reaction with the prepolymer is carried out in a solvent, the resulting block copolymer solution may... 

Another method which can be used for the synthesis of polyfester ester) s is end-linking. For example, an aliphatic polyester diol with the hydroxyl end groups and PET or PBT prepolymer can be coupled by reaction with diisocyanate. 

Two-stage crosslinking, in which in the first stage is the synthesis of a prepolymer containing two isocyanato endgroups in the classical way of reaction (a diol either of low or of high molecular weight with an excess of diisocyanate) and the second step to form the network, can be accomplished by... 

Instead of the diols above, Maji et al. [56] evaluated a hydroxyl functional polyester-polyurethane prepolymer prepared by the ester formation of diethylene glycol with adipic acid and subsequent urethane formation with the 2,4-toluene diisocyanate (TDI) reaction with the excess hydroxyls on the polyester (Urepan 600 prepared by M/s Rhein... 

One-part polyurethane adhesives can also correspond to prepolymers with isocyanate functions blocked reversibly (due to reaction with oximes, phenols, etc.). The isocyanate groups are then regenerated, either by heating to a more or less high temperature, or by substitution of the blocking agent by a diol (oligomer, at least partly) (O Fig. 14.18). 

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